Stabilized dry rosin size



t atented Sept. E, 3942 entree s'rArEs PATENT orrice I STABILIZED DRY ROSIN SIZE Arthur C. Dreshfield, Wilmington, Del., assignor to Hercules Powder Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application December 4, 1940, Serial No. 368,448

' 9 Claims.

' shipment, the type of dry-rosin size prepared by spray-drying saponified or partially s'aponified rosin being especially desirable because of its low density and high rate of solution in water.

The dry forms of rosin size, particularly the type formed by spray-drying, however, are disadvantageous in that they have a strong tendency to oxidize and spontaneously decompose in the presence of air. Where, as is not uncommon, some free rosin is contained in the size, there is even a greater tendency to oxidize. Such oxidation, and consequent heating, is not only highly deleterious to the size itself but presents a considerable fire hazard during storage and shipment.

I have now found that dry rosin sizes comprising saponified rosin orsaponified abietic acid may be effectively stabilized against oxidation by the addition of a small proportion of a long periods of time without danger of decomposition by oxidation or spontaneous combustion.

The which may be employed in preparing stabilized dry rosin size compositions according to the invention may be defined by the general formula naphthylamine, (4 ethoxyl phenyl) alphasecondary diarylamine anti-oxidants naphthylamine, 4,4 -dimethoxy-diphenylamine, 4,4 dimethoxy 3- methyl diphenylamine, 3-methoxy 4' methyl-diphenylamine, 3-methoxy-diphenylamine, 3-isopropoxy-diphenylamine,

4,4 dichloro diphenylamine, p-xenyl alpha naphthylamine, 1,1-dimethyl-di-beta-naphthylamine, 4-hydroxy 4' m'ethoxy-diphenylamine, 4-amino-diphenylamine, 4 hydroxy diphenylamine, 4,4'-di-isopropyl-diphenylamine, 4-butyldiphenylamine, 4,4'-di-tert. butyl-diphenylamine, 5,5'-dimethyl acridane, etc.

While any of the secondary diarylamines having the above formula may be employed as antioxidants for dry rosin size, I prefer to employ those in which the aromatic radicals are phenyl,

naphthyl, lower alkyl-phenyl, lower-alkoxyphenyl, lower alkoxy-alkyl-phenyl or tetrahydronaphthyl radicals. 'Such secondary diarylamines are in general more readily available and in all ordinary purposes if it resists oxidation for about 48 hours when subjected to an accelerated oxidation treatment known as the "Mackay test. This treatment consists in placing a sample of the stabilized size in a wire basket suspended in a water-jacketed chamber maintained at a temperature of C. A small volume of air is passed continuously through the chamber for the desired length of time, during which time the temperature of the sample.

which is a measure of the oxidation, is accurately determined.- Dry rosin size containing no anti-oxidant will oxidize to a considerab e extent,

'i. e., its temperature will rise considerably above 100 C., and it may even ignite and burn when subjected to this test over a period of about 48 hours, while a size stabilized accordingto "anti-oxidant 'to secure goodstabilization';

the invention will undergo substantially no oxldation.

-The optimum proportion of anti-oxidant also depends upon the composition of the size itself, a somewhat larger proportion being required for sizes containing free alkali or free rosin. Thus. for example, a neutral saponified rosin size may be rendered stable to oxidation determined by the 48-hour Mackay test by the addition of,0.05 per cent by weight of phenyl-beta-naphthylamine, whereas a size containing 0.3-0.6 per cent by weight of free alkali requires the addition of 0.15 per cent by weight of pheny1-beta-naphthyl-. amine to secure such a degree of stabilization. Similarly, sizes containing 5.0 and. 10.0 per cent by weight of free rosin may require the use of 0.2 and 0.6 per cent by weight, respectively, of the The type of dry size, 1. e., whether it has been prepared from wood rosin, gum rosin. or rosin which has been heat-treated to effect partial decarboxylation. is also of influence on the proportion of anti-oxidant to be used. Thus, sizes compris ing saponified gum rosin usually required a somewhat larger proportion of the anti-oxidant than a the other types. In general. however. itwill be found that from about 0.1 to about 1.5 per cent of the anti'oxidant, based on the Weight of rosin used in preparing the size, will be suificient to render any dry size substantially resistant to oxielation. I

The anti-oxidant may be incorporated with the size at any convenient time during the process for the production of the size, by treatment of the size after it is produced, or by treatment of the rosin prior to its saponification. Ordinarily, however, the anti-oxidant will desirably and most effectively be added to the size during its preparation by the saponification of rosin. A particularly convenient mode of effecting such addition consists in dissolving the anti-oxiclant in a Suitable solvent and adding the resultant solution to the mixture of water. alkali, and rosin in the reaction ve ssel in which the 'saponification reaction is carried out. 7 Thus, for example, about 0.2 per cent of phenyl-beta-naphthylamine, based on the weight of the rosin employed, may be dissolved in alcohol and added to a mixture of rosin, water, and sodium hydroxide so proportioned as to produce a size containing about 5.0 per cent free rosin. either before or during the saponification reaction. Upon completion of the reaction, the mixture may be desiccated by spray or drum drying to produce a dry size having the anti-oxidant uniformly distributed therethrough.

The following table presents comparative data illustrative of the degree of stabilization secured by the use of a number of anti-oxidants of the present class. In each experiment, approximately 40 parts of gum rosin was saponified with parts of sodium hydroxide in the form of a 39 per cent aqueous solution. When the .saponification reaction was about one-half completed, the anti-oxidant. in the proportion given in the table and dissolved in paraffin oil, was added to the reaction mixture. Upon completion of the reaction, the mixture was spray-dried to form a dry powder having the anti-oxidant uniformly distributed throughout. A sample of the composition so prepared was then tested for ease of oxidation by the 48-hour Mackay test as well as bya standard oxygen demand test in'an oxygen absorption train. The oxygen demand is expressed as the per cent by weight oxygen absorbed over a four-hour period.

, Table Anti-oxidant Expt y n No. demand Mackay test Niune Percent Percent 1 None (control) i i 3. 79 Burned in 13 hrs.

2 Ihenyl-beta-naphthyl- 0.3 0. 76 Stable.

amino.

3 Dlphcnylainino 0.5 0. 01 Do.

4 4, 4-dimcthoxy;diphcn- 0.5 0. 49 D0.

ylaminc.

5 Ditolylmnincs 0. 5 l. 57 Do.

a lhunyl -huta ar totra- 0. 5 0. 42 D0.

hydronaphthylamine. Y

7 4 isopropoxy diphen- 0.5 O. 42 Do.

ylainino.

8 3 mothoxy diphcnyl- 0. 5 0.71 Do.

amino.

9 4, 4 dimethoxy 3 0.5 0.48 Do.

nvth yl diphenylaml0 3-niethoxy-4 methyl- 0.5 0.72 l)o.

diplienylmnine.

ll Alpha beta dinaph 0.5 0. 70 Do.

thylamine.

l2 I)i-beta-mphthylamlne 0.5 0. 83 D0.

13 4-hydroxy-diphenylam- 0.5 0. 33 llo.

Int.

14 p lolyl alpha nnph 0. 5 0. 69 Do.

thylrimlnc.

l5 5.5-(1imetliyl-acridnno 0. 5 1.55 Do.

Other modes of applying the principle of my invention may be employed instead of those explained, change being made as regards the materials employed, provided the ingredients stated by any of the appended claims or the equivalent of such stated ingredients be employed.

This application is a continuation-in-part of my co-pending application Serial No. 152,194, filed July 6, 1937.

What I claim and desire to protect by Letters Patent is:

1. A stabilized dry size composition comprising saponified rosin and, as an anti-oxidant therefor, a secondary diarylamine having the general formula 11 R-I lR' wherein R and R each represents an aromatic radical, said diarylamine being present in an amount suflicient to render the composition substantially resistant to oxidation.

2. A stabilized dry size composition comprising saponified rosin and, as an anti-oxidant therefor,

a secondary diarylamine having the general formula III R-N-R wherein R and R each represents an aromatic radical selected from the group consisting of phenyl, naphthyl, lower alkyl-phenyl, lower alkoxy-phenyl, lower alkoxy-alkyl-phenyl, and tetrahydronaphthyl radicals, said diarylamlne being present in an amount sufficient to render the composition substantially resistant to oxidation.

3. A stabilized dry size composition comprising saponified rosin, free rosin, and, as an antioxidant therefor, a secondary diarylarnine having the general formula RNR' wherein R and R each represents an aromatic radical selected from the group consisting of phenyl, naphthyl, lower alkyl-phenyl, lower alkoxy-phenyl, lower alkoxy-alkyl-phenyl, and tetrahydronaphthyl radicals, said diarylarnine being present in an amount sufficient to render 7. A stabilized dry size composition comprising saponified rosin, free rosin, and, as an antioxidant therefor, phenyl-alpha-naphthylamine' in an amount sufiicient to render the composition substantially resistant to oxidation.

8. A stabilized dry size composition comprising saponified rosin and, as an anti-oxidant therefor, diphenylamine in an amount sufficient to render the composition'substantially resistant to oxidation.

9. A stabilized dry size composition comprising saponified rosin, free rosin, and, as an antioxidant therefor, diphenylamine in an amount sufiicient to render the composition substantially resistant to oxidation.

AR'I'I-IUR C. DRESHFIELD, 

